CN1161412C - Polypropylene graft copolymers with improved scratch and mar resistance - Google Patents
Polypropylene graft copolymers with improved scratch and mar resistance Download PDFInfo
- Publication number
- CN1161412C CN1161412C CNB998043346A CN99804334A CN1161412C CN 1161412 C CN1161412 C CN 1161412C CN B998043346 A CNB998043346 A CN B998043346A CN 99804334 A CN99804334 A CN 99804334A CN 1161412 C CN1161412 C CN 1161412C
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- Prior art keywords
- ethene
- olefin
- weight
- alpha
- propylene
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- XJELOQYISYPGDX-UHFFFAOYSA-N ethenyl 2-chloroacetate Chemical compound ClCC(=O)OC=C XJELOQYISYPGDX-UHFFFAOYSA-N 0.000 description 1
- GFJVXXWOPWLRNU-UHFFFAOYSA-N ethenyl formate Chemical compound C=COC=O GFJVXXWOPWLRNU-UHFFFAOYSA-N 0.000 description 1
- XEKOWRVHYACXOJ-UHFFFAOYSA-N ethyl acetate Substances CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 1
- VXNZUUAINFGPBY-UHFFFAOYSA-N ethyl ethylene Natural products CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N ferric oxide Chemical compound O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 239000001530 fumaric acid Substances 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- PYGSKMBEVAICCR-UHFFFAOYSA-N hexa-1,5-diene Chemical compound C=CCCC=C PYGSKMBEVAICCR-UHFFFAOYSA-N 0.000 description 1
- DPUXQWOMYBMHRN-UHFFFAOYSA-N hexa-2,3-diene Chemical compound CCC=C=CC DPUXQWOMYBMHRN-UHFFFAOYSA-N 0.000 description 1
- 238000005984 hydrogenation reaction Methods 0.000 description 1
- 125000002768 hydroxyalkyl group Chemical group 0.000 description 1
- 150000003949 imides Chemical class 0.000 description 1
- 239000003701 inert diluent Substances 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 238000011005 laboratory method Methods 0.000 description 1
- 239000004310 lactic acid Substances 0.000 description 1
- 235000014655 lactic acid Nutrition 0.000 description 1
- 235000012204 lemonade/lime carbonate Nutrition 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- FQPSGWSUVKBHSU-UHFFFAOYSA-N methacrylamide Chemical compound CC(=C)C(N)=O FQPSGWSUVKBHSU-UHFFFAOYSA-N 0.000 description 1
- HZVOZRGWRWCICA-UHFFFAOYSA-N methanediyl Chemical compound [CH2] HZVOZRGWRWCICA-UHFFFAOYSA-N 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 238000005065 mining Methods 0.000 description 1
- KKFHAJHLJHVUDM-UHFFFAOYSA-N n-vinylcarbazole Chemical compound C1=CC=C2N(C=C)C3=CC=CC=C3C2=C1 KKFHAJHLJHVUDM-UHFFFAOYSA-N 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- FATBGEAMYMYZAF-KTKRTIGZSA-N oleamide Chemical compound CCCCCCCC\C=C/CCCCCCCC(N)=O FATBGEAMYMYZAF-KTKRTIGZSA-N 0.000 description 1
- 229940113162 oleylamide Drugs 0.000 description 1
- QMMOXUPEWRXHJS-UHFFFAOYSA-N pent-2-ene Chemical group CCC=CC QMMOXUPEWRXHJS-UHFFFAOYSA-N 0.000 description 1
- YWAKXRMUMFPDSH-UHFFFAOYSA-N pentene Chemical group CCCC=C YWAKXRMUMFPDSH-UHFFFAOYSA-N 0.000 description 1
- 150000002978 peroxides Chemical class 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000010926 purge Methods 0.000 description 1
- 239000007870 radical polymerization initiator Substances 0.000 description 1
- 239000002516 radical scavenger Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- FZHAPNGMFPVSLP-UHFFFAOYSA-N silanamine Chemical compound [SiH3]N FZHAPNGMFPVSLP-UHFFFAOYSA-N 0.000 description 1
- 239000012748 slip agent Substances 0.000 description 1
- 150000003440 styrenes Chemical class 0.000 description 1
- 150000005846 sugar alcohols Polymers 0.000 description 1
- 229920003051 synthetic elastomer Polymers 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 238000003856 thermoforming Methods 0.000 description 1
- 229920002725 thermoplastic elastomer Polymers 0.000 description 1
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 1
- 239000010456 wollastonite Substances 0.000 description 1
- 229910052882 wollastonite Inorganic materials 0.000 description 1
- 210000002268 wool Anatomy 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L51/00—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
- C08L51/06—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers grafted on to homopolymers or copolymers of aliphatic hydrocarbons containing only one carbon-to-carbon double bond
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
- C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L23/10—Homopolymers or copolymers of propene
- C08L23/12—Polypropene
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2207/00—Properties characterising the ingredient of the composition
- C08L2207/02—Heterophasic composition
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
- C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L23/04—Homopolymers or copolymers of ethene
- C08L23/06—Polyethene
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Graft Or Block Polymers (AREA)
- Manufacture Of Macromolecular Shaped Articles (AREA)
- Paints Or Removers (AREA)
- Laminated Bodies (AREA)
Abstract
A polymer composition with improved scratch and mar resistance contains (1) a graft copolymer comprising a backbone of a propylene polymer material having graft polymerized thereto at least one vinyl monomer capable of being polymerized by free radicals, and (2) an additive selected from the group consisting of (a) about 0.5 % to about 10 % of at least one low molecular weight ethylene polymer or a functionalized derivative thereof, and (b) a combination of (i) about 0.5 % to about 10 % of at least one of the low molecular weight ethylene polymers in (a) and (ii) about 0.5 % to about 10 % of inorganic microspheres, based on the total weight of the composition. Optionally the composition can also contain a compatible agent such as an unsaturated carboxylic acid-functionalized propylene polymer material. The composition can optionally contain about 2 % to about 30 % of one or more rubber components, about 15 % to about 50 % of a broad molecular weight distribution propylene polymer material, or a combination of the two.
Description
FIELD OF THE INVENTION
The present invention relates to contain the composition of the graft copolymer of amphoteric polymeric material, one or more vinyl monomers of graft polymerization on the described amphoteric polymeric material.
The background of invention
The scratch resistance of the moulded parts that is made by polyolefine and scratch property are poor.That is to say that the slight friction of object (as nail) just abrades or scratch its surface easily.With modified polyolefin (as be grafted with one or more vinyl monomers, as vinylbenzene or acrylic compounds, amphoteric polymeric material) the also performance scratch resistance and the scratch property of going on business.If add rubber in these graft copolymers, then the scratch resistance of the goods that made by these multipolymers and scratch property can descend usually.
As european patent application 832,925 is described, by adding independent lubricant (as polysiloxane) or combining scratch resistance and the scratch property that can improve thermoplastic olefin (the elastomeric uncrosslinked blend of crystalline olefin polymers and olefin polymer) with aliphatic acid amides (as erucicamide and/or oleylamide).
Need to improve the scratch resistance and the scratch performance that contain the graft copolymer of graft polymerization vinyl monomer on amphoteric polymeric material main chain and this main chain, still take into account favorable mechanical performance and high surface gloss simultaneously.
The general introduction of invention
The present composition comprises: (1) a kind of graft copolymer, it comprises the amphoteric polymeric material main chain, graft polymerization has at least a vinyl monomer that can carry out radical polymerization on this main chain, and the content of polymerization single polymerization monomer is about 10-120 part in per 100 parts of amphoteric polymeric materials; (2) a kind of additive, it is selected from, gross weight by composition, (a) at least a number-average molecular weight of about 0.5%-10% is about the low-molecular ethylene polymers of 300-5000 or its functionalized derivative and (b) at least a low-molecular ethylene polymers (a) of (i) about 0.5%-10% and the mixture of (ii) about 0.5-10% inorganic microspheres.Said composition also can randomly contain coupling agent, as the propene polymer of undersaturated carboxylic-acid functional.
Said composition also can randomly contain the have an appointment amphoteric polymeric material of one or more rubber components of 2-30%, about 15-50% wide molecular weight distribution or both mixtures.
The moulded parts that makes with these compositions has the glossy surface, has much higher scratch resistance and scratch property than above-mentioned typical graft multipolymer.
The detailed description of invention
The component of the present composition (1) is a kind of graft copolymer, and it comprises amphoteric polymeric material main chain and at least a vinyl monomer that can carry out radical polymerization that is grafted on this main chain.
Amphoteric polymeric material as the graft copolymer main chain can be:
(1) isotactic index is greater than 80, better the alfon of about 85-99;
(2) propylene and a kind of multipolymer that is selected from the ethene and the alkene of alpha-olefin with 4-10 carbon atom, condition is when described alkene is ethene, the maximum level of polymerising ethylene is about 10%, better about 4%, when described alkene is when having the alpha-olefin of 4-10 carbon atom, its polymeric maximum level is about 20 weight %, better about 16 weight %, and the isotactic index of described multipolymer is greater than 85;
(3) propylene and two kinds of terpolymers that are selected from the ethene and the alkene of alpha-olefin with 4-8 carbon atom, condition is that the maximum polymerization content with alpha-olefin of 4-8 carbon atom is 20 weight %, better about 16 weight %, when ethene is one of the alkene of copolymerization, the maximum level of polymerising ethylene is 5 weight %, better about 4 weight %, the isotactic index of described terpolymer is greater than 85;
(4) a kind of olefin polymer compositions, it comprises:
(a) about 10-60 weight %, better about 15-55 weight % isotactic index is greater than 80, the alfon of better about 85-98, or be selected from (i) propylene and ethene, (ii) propylene, ethene and have the alpha-olefin of 4-8 carbon atom and (iii) propylene and have the monomeric multipolymer of the alpha-olefin of 4-8 carbon atom, the content of polypropylene is greater than 85 weight % in the multipolymer, better about 90-99%, isotactic index is greater than 85;
(b) about 5-25 weight %, better about 5-20 weight % ethene and propylene or have the multipolymer of the alpha-olefin of 4-8 carbon atom are insoluble to dimethylbenzene at this multipolymer of envrionment temperature;
(c) about 30-70 weight %, better about 40-65 weight % is selected from (i) ethene and propylene, (ii) ethene, propylene and have the alpha-olefin of 4-8 carbon atom, (iii) ethene and have the monomeric elastocopolymer of the alpha-olefin of 4-8 carbon atom, this multipolymer randomly contains the 0.5-10 weight % polymeric diene of having an appointment, the polymeric ethylene content is less than 70 weight %, better about 10-60 weight %, better about 12-55 weight %, this multipolymer is dissolved in dimethylbenzene at ambient temperature, and the limiting viscosity that records under 135 ℃ in naphthane is about 1.5-4.0dl/g;
Wherein (b) and total amount (c) account for about 50-90% of olefin polymer compositions total amount, and weight ratio (b)/(c) is preferably 0.1-0.3 less than 0.4, and described composition makes by two-stage polymerization at least, and its modulus in flexure is less than 150MPa; Perhaps
(5) a kind of thermoplastic olefin, it comprises:
(a) about 10-60%, better about 20-50% isotactic index is greater than 80 alfon, or be selected from (i) ethene and propylene, (ii) ethene, propylene and have the alpha-olefin of 4-8 carbon atom, (iii) ethene and have monomeric a kind of multipolymer of the alpha-olefin of 4-8 carbon atom, the content of polymeric propylene is greater than 85% in this multipolymer, and isotactic index is greater than 85;
(b) about 20-60%, better about 30 one 50% are selected from (i) ethene and propylene, (ii) ethene, propylene and have the alpha-olefin of 4-8 carbon atom, (iii) ethene and have the monomeric amorphous copolymer of the alpha-olefin of 4-8 carbon atom, this multipolymer also randomly contains the 0.5-10% polymeric diene of having an appointment, the content of polymeric ethene is less than 70%, and this multipolymer is dissolved in dimethylbenzene at ambient temperature; With
(c) about 3-40%, better about 10-20% ethene and propylene or have the multipolymer of the alpha-olefin of 4-8 carbon atom are insoluble to dimethylbenzene at this multipolymer of envrionment temperature;
Wherein the modulus in flexure of this thermoplastic olefin is greater than 150MPa, but less than 1200MPa, better about 200-1100MPa, preferably about 200-1000MPa.
Room temperature or envrionment temperature are about 25 ℃.
The alpha-olefin with 4-8 carbon atom that is used for preparation (4) and (5) comprises, for example 1-butylene, 1-amylene, 1-hexene, 4-methyl-1-pentene and 1-octene.
When using diene, it is divinyl, 1 normally, 4-hexadiene, 1,5-hexadiene or ethylidene norbornene.
Amphoteric polymeric material (4) and (5) can make by two-stage polymerization at least, in the first step, component (a) with propylene, propylene and ethene, propylene and alpha-olefin or propylene and ethene and alpha-olefines polymerization synthetic (4) or (5), in step subsequently, in the presence of (a), the polymerization of mixtures of ethene and propylene, ethene and alpha-olefin or ethene and propylene and alpha-olefin and optional diene become the component (b) of (4) or (5) and (c).
Described polymerization can use independent reactor to carry out in the mode of liquid phase, gas phase or liquid-gas phase, and all these polymerization methodses all can be intermittently to carry out or carry out continuously.For example, can use propylene liquid, and in vapour phase polymerization component (b) and (c), except the propylene partly degassed, need not intermediate steps as thinner polymeric component (a).All vapour phase polymerizations are methods preferably.
The manufacture method of amphoteric polymeric material (4) is described in detail in United States Patent (USP) 5,212, and 246 and 5,409,992, these patents are drawn at this and are reference.The manufacture method of amphoteric polymeric material (5) is described in detail in United States Patent (USP) 5,302, and in 454 and 5,409,992, these patents are drawn at this and are reference.
Alfon is a propylene polymer main chain material preferably.
The monomer that can be grafted on the amphoteric polymeric material main chain can be any monomer ethylene based compound that can carry out radical polymerization, therein ethylene base group H
2C=CR-(R is H or methyl) is connected on the straight or branched aliphatic chain or is connected on the monocycle or polynuclear compound replacement or unsubstituted aryl, heterocycle or alicyclic ring.Concrete substituting group can be alkyl, hydroxyalkyl, aryl and halogen.Described vinyl monomer belongs to a kind of in the compound of following type usually: aromatics, heterocycle or the alicyclic compound of (1) vinyl substituted, comprise vinylbenzene, vinyl naphthalene, vinyl pyridine, vinyl pyrrolidone, vinylcarbazole and homologue thereof, as alpha-methyl styrene with to vinyltoluene, methyl chloride vinylbenzene, to t-butyl styrene, ethylene methacrylic yl pyridines and ethylethylene yl pyridines; (2) vinyl acetate of aromatic carboxylic acid and saturated aliphatic carboxylic acid comprises vinyl formate, vinyl-acetic ester, vinyl chloroacetate, cyanoacetic acid vinyl acetate, propionate and vinyl benzoate; (3) unsaturated aliphatic nitrile and unsaturated carboxylic acid and derivative thereof, as vinyl cyanide, methacrylonitrile, acrylamide, Methacrylamide, vinylformic acid, acrylate such as methyl acrylate, ethyl ester, hydroxyl ethyl ester, 2-ethylhexyl and butyl ester, methacrylic acid, ethyl propylene (ethacrylic) acid, methacrylic ester such as methyl methacrylate, ethyl ester, butyl ester, benzyl ester, phenethyl ester, phenoxy ethyl, oxyethyl group propyl ester and hydroxypropyl acrylate, maleic anhydride and N-phenylmaleimide.Can use the multiple monomer of identical or type inequality.Account for methyl methacrylate and the methyl acrylate of 0.5-10% by total monomer weight methyl acrylate or methyl methacrylate, perhaps methyl methacrylate and methacrylic acid are grafted monomer preferably.
Polymerization single polymerization monomer accounts for 10-120 part in per 100 parts of amphoteric polymeric materials, better is about 30-95pph.
In the graft polymerization process, monomer also aggregates into a certain amount of free or polymers grafted not.Amphoteric polymeric material is as external phase or matrix phase in the form of graft copolymer, grafting and not the grafted polymerization single polymerization monomer as disperse phase.
Can use any manufacturing graft copolymer in the several different methods.A kind of in these methods comprises with superoxide or as other compound treatment amphoteric polymeric material of radical polymerization initiator, forms active grafting site position thereon, perhaps forms active grafting site position by high-energy ionization radiation irradiation.Form active grafting site position by chemical treatment or radiation treatment on polymkeric substance, cause forming free radical on polymkeric substance, trigger monomer carries out polymerization on these some positions.The graft copolymer that the grafting method that causes with superoxide makes is preferably.
Contact the method for making graft copolymer with a kind of vinyl monomer with free radical polyalcohol initiator (as organic superoxide) and polypropylene and be described in detail in United States Patent (USP) 5,140, in 074, this patent is drawn at this and is reference.The irradiation olefin polymer is handled it with a kind of vinyl monomer subsequently at least and the method for making graft copolymer is described in detail in United States Patent (USP) 5,411, and in 994, this patent is drawn at this and is reference.
The component of the present composition (2) can be at least a number-average molecular weight (M
n) be about the low-molecular ethylene polymers of 300-5000.Also can use these polyvinyl functional derivatives, as its phosphoric acid ester of derivative of hydroxylation or ethoxylation, perhaps monocarboxylic derivative or toxilic acid grafted linear ethylene polymkeric substance.Ethene polymers or polyvinyl mixture account for the 0.5-10% of composition total weight, better account for 2-5%.
Component (2) can also be at least a above-mentioned low-molecular ethylene polymers of (i) about 0.5-10% and (ii) account for composition total weight 0.5-10%, better account for the mixture of the inorganic microspheres of composition total weight 1-5%.Described inorganic microspheres can be silica-alumina ceramal, alkali metal aluminosilicate pottery or glass, and can randomly be coated with treating compound, as aminosilane.
Described composition also can contain compatilizer, for example use α, beta-unsaturated carboxylic acid or alicyclic carboxylic acid and derivative thereof are (as vinylformic acid, methacrylic acid, toxilic acid, fumaric acid, methylene-succinic acid, bridged ring (2,2,1)-5-heptene-2,3-carboxylic acid and suitable-4-hexanaphthene-1,2-carboxylic acid and acid anhydrides thereof, ester, acid amides and imide) polypropylene of modification.With the maleic anhydride of difference amount or the polypropylene of toxilic acid modification is preferably, and it can be available from for example EastmanChemical Company and Aristech Chemical Corporation.By polymer-modified gross weight, modified polypropene generally contains 0.2-10% toxilic acid or maleic anhydride approximately.When using compatilizer, it accounts for the 0.2-4% of composition total weight, better accounts for 0.5-2%.
Randomly, composition also can contain and accounts for composition total weight 2-30%, better accounts for one or more rubber components of 5-30%, and/or accounts for composition total weight 15-50%, better accounts for the amphoteric polymeric material of the wide molecular weight distribution of 40-50%.
Described rubber components is selected from (i) olefin copolymer rubber, (ii) mono alkenyl aromatic hydrocarbon-conjugated diene block copolymer rubber and (iii) one or more in the nuclear-shell rubber.Any in these rubber components all can have acid or anhydride functional group or can not contain these functional groups.Rubber components is (i) or (ii) preferably, independent this component or both mixtures.
Suitable olefin copolymer rubber comprises, for example saturated olefin copolymer rubber is as ethylene/propene monomer rubber (EPM), ethene/1-octene rubber and ethene/1-butylene rubber; With undersaturated olefin copolymer rubber, as ethylene/propylene/diene monomer rubber (EPDM).Olefin copolymer rubber is ethylene/propene, ethene/1-butylene and ethene/1-octene copolymer preferably.
Described mono alkenyl aromatic hydrocarbon-conjugated diene block copolymer can be A-B structure (being diblock), line style A-B-A structure (i.e. three blocks), radial (A-B)
nThe thermoplastic elastomer of the mixed type of (wherein n=3-20%) or these structures, wherein each A block is a mono alkenyl aromatic hydrocarbon polymer blocks, each B block is undersaturated diblock rubber.The multipolymer of such various grades all is commercially available.Different grades has molecular weight and the different mono alkenyl aromatic hydrocarbon and the ratio of rubber of different structures, different centre and end block.Also can carry out hydrogenation to segmented copolymer.Typical mono alkenyl aromatic hydrocarbon monomer is the straight or branched ring-alkylated styrenes and the Vinyl toluene of vinylbenzene, the cyclosubstituted 1-4 of a having carbon atom.Better be vinylbenzene.Suitable conjugated diolefine comprises, for example divinyl and isoprene.Segmented copolymer is hydrogenant styrene/ethylene-1-butylene/styrene triblock copolymer preferably.
Weight-average molecular weight (the M of segmented copolymer
w) generally be about 45,000-260,000g/mol, molecular-weight average is about 50 preferably, 000-125,000g/mol is because its composition that makes has good shock strength and inflexible over-all properties.Equally, although can use the segmented copolymer with unsaturated rubber block and saturated rubber block, multipolymer has saturated diblock rubber preferably, and this is to consider for the shock strength of taking into account the composition that contains this multipolymer/inflexible equally.The weight ratio of mono alkenyl aromatic hydrocarbon and conjugated diene rubber is about 5/95-50/50 in segmented copolymer, better is about 10/90-40/60.
Nuclear-shell rubber components comprises the crosslinked rubber phase small-particle that is surrounded by compatible shell (normally glassy polymers or multipolymer).Described nuclear is elastoprene normally, as divinyl or synthetic polyisoprene or polyacrylic ester.Normally two or more are selected from the polymer of monomers of vinylbenzene, methyl methacrylate and vinyl cyanide to described shell.Better nuclear-shell rubber has the nuclear of polyacrylic ester.
Suitable impact modifying agent comprises, for example available from Engage 8150 or the Engage 8200 ethene/1-octene copolymer of DuPont-Dow Elastomers; Available from Miles, the EPM 306P ethylene/propene copolymer of the Polysar RubberDivision of Incorporated; With available from the usefulness of Shell Chemical Company maleic anhydride modified Kraton RP6912 styrene/ethylene-propylene/styrene triblock copolymer rubber and Kraton FG1901X styrene/ethylene-1-butylene/styrene triblock copolymer rubber.
Another kind of optional component is the amphoteric polymeric material (BMWD PP) of wide molecular weight distribution, its M
w/ M
nBe about 5-60, better be about 5-40; Melt flow rate (MFR) is about 0.5-50g/10min, better is about 1-30g/10min; At 25 ℃ of dimethylbenzene insolubless more than or equal to 94%, better more than or equal to 96%, more preferably greater than or equal 98%.Amphoteric polymeric material with wide molecular weight distribution can be alfon or carry out impact modified alfon with ethylene/propylene rubber that described alfon has wide molecular weight distribution.
Described BMWD PP can load on Ziegler-Natta catalyst on the magnesium halide of activity morphology in the presence of, going on foot successively with at least two, polymerization makes.Independently with in the successive step carry out polymerization in two steps, per step polymerization is to carry out in the presence of the polymkeric substance of previous step and catalyzer.
Can carry out liquid polymerization in the existence of inert diluent or not, or carry out gas phase or liquid-vapour phase polymerization according to known technology intermittence or successive method to carry out polymerization, better be vapour phase polymerization.The preparation method of BMWD PP is described in detail in United States Patent (USP) 5,286, and in 791, this patent is drawn at this and is reference.
Also can contain other additive in the present composition, as pigment, nucleator, pigment dispersion aids, primary antioxidant and auxiliary antioxidant, photostabilizer, acid scavenger, surface slip agent and filler, as talcum powder, lime carbonate and wollastonite.
Can use methods known in the art, comprise that thermoforming, injection moulding, sheet material are extruded, section bar is extruded and blowing is made useful goods with the present composition.
The test method that is used to estimate molded sample has:
Izod impact strength ASTM D-256A
Tensile strength ASTM D-638-89
Elongation at yield rate ASTM D-638-89
Elongation at break ASTM D-638-89
Modulus in flexure ASTM D-790-86
Flexural strength ASTM D-790-86
Melt flow rate (MFR) (230 ℃, 2.16kg) ASTM D-1238
Use Ford Laboratory Test Method BN 108-13 (scratch resistance) to measure resistance to marring and scratch property.Equipment comprises that the wisp of several heavy burdens is shelved on the surface of sample.The wisp that is used to scratch test is the press polished steel ball of 1.0mm, and the wisp that is used for scoring test is the steel ball of 7.0mm.Described wisp has different loads, so that following proof force is applied on the specimen surface: 7.0 newton (N), 6.0N, 3.0N, 2.0N, 0.6N.Subsequently along dilatory this wisp of panel.Check all cuts and by 1-5 level evaluation, 1 grade is no marking, 5 grades for having severe marking.The improvement of relative comparison sample is the standard that can accept the result.Use the painted sample of black pigment, because observing cut than easier on the surface in other color with bore hole on the black surface.
On smooth (not cut) sample, read all glossiness readings with 20 degree glossmeters.
Use CM-5 type Atlas AATCC scoring test machine to carry out the test of Chrysler crocking glossiness according to Chrysler laboratory method LP-463PB-54-01.Dry Bon-Ami sanitising agent is applied in 4 " * 6 " on half surface of molded plate.On the cylindrical acrylic acid or the like finger-type thing of scoring test machine, be coated with available from Atlas Electric Devices Co. 2 " * 2 " the green felt of 14-9956-000 of size.Scribbling 10 times (10 round trips) of friction on the molded plate of sanitising agent with wool felt.The scratch district of molded plate and the number place in scratch district measure 20 ° of glossiness.Not abrade the maximum glossiness data in district as original glossiness.To abrade the minimum glossiness in district as abrasive glossiness.% gloss keeps or resistance to marring is that abrasive glossiness multiply by 100 divided by original glossiness.
Use CM-5 type Atlas AATCC scoring test machine, carry out the test of crocking glossiness according to Ford laboratory test methods B1161-01 (anti scuffing that is used for automotive coatings is measured).A slice is placed on available from the green felt of the onesize 14-9956-000 of Atlas Electric Devices Co. available from 50 * 50mm of Minnesota Mining and Manufacturing Company square 281Q Wetordry Production Polishing Paper (3 micron orders but not 2 microns standard level), and a side that makes polishing paper tape abrasive material outwardly.These two squares are fixed on the finger-type thing of scoring test machine, felt is between finger-type thing and the polishing paper.These scoring test facility have cylindrical acrylic acid or the like, brass or wooden finger-type thing, and diameter 16mm can apply the power of 9N and have about 100mm stroke to testing surface.After mensuration is taken temperature 20 ° of glossiness of face, this surface is carried out the friction of 10 round trips with the scoring test machine.In 20 ° of glossiness of the direction detection frictional belt parallel with scoring test machine friction stroke, and the record least reading.% gloss keeps or resistance to marring is that 20 ° of glossiness of frictional belt multiply by 100 divided by 20 ° of original glossiness.
Isotactic index is defined as the percentage ratio of the insoluble olefin polymer in the dimethylbenzene.In the dissolving weight percentage of room temperature olefin polymer in dimethylbenzene is following recording: be equipped with in room temperature in the container of agitator 2.5 gram polymer dissolution in 250 milliliters of dimethylbenzene, while stirring with it 135 ℃ of heating 20 minutes.When continuing stirring, solution is cooled to 25 ℃, it is left standstill 30 minutes subsequently, make solid precipitation.With filter paper elimination solid, heating evaporation rest solution in nitrogen gas stream is dried to constant weight with solid residue under 80 ℃ vacuum.The weight percentage that is insoluble to the polymkeric substance of dimethylbenzene in room temperature is the isotactic index of polymkeric substance.The data that obtain in this way with boiling n-heptane extraction, basic identical by the isotactic index that the mensuration that is defined as the polymkeric substance isotactic index obtains.
Limiting viscosity records in naphthane at 135 ℃.
Below all among the embodiment, before test, ASTM T shape bar is regulated 48-96 hour under 23 ℃ and 50% relative humidity.Before molding sheet material is used for cut/scoring test, with each sample extrude pellet about 175 °F (80 ℃) dry at least 1 hour, but dried overnight usually.The molding sheet material that will be used for cut/scoring test before test wore out 48 hours under envrionment temperature and humidity at least.
In this manual except as otherwise noted, otherwise all parts and percentage number average are by weight.
Embodiment 1
Present embodiment explanation low molecular weight polyethylene is to the scratch resistance of the composition that contains 5% rubber and graft copolymer and the influence of scratch property, and described graft copolymer comprises grafted methyl methacrylate/methyl acrylate copolymer (MMA/MeAc) on alfon main chain and the main chain.
Present embodiment and below among the embodiment, have following performance as the alfon of trunk polymer: spherical, the melt flow rate (MFR) (MFR) under 230 ℃ and 2.16kg load is 9.8dg/min, is insoluble to dimethylbenzene in room temperature 96.1%.
The graft polymerization procedure of using foregoing superoxide to cause is grafted on monomer (counting 95.6%MMA and 4.4%MeAc by total monomer weight) on this polypropylene backbone under 114 ℃ grafting temperature.Add 95 weight parts monomers in per 100 weight part polypropylene.Will be available from the Lupersol PMS (solution of 50% t-butyl peroxy-2-ethylhexanoate in petroleum spirit) of Elf Atochem as peroxide initiator.Monomer fed in raw material 95 minutes with the speed of 1pph/min.The mol ratio of monomer and initiator is 120.After adding monomer, temperature risen to 140 ℃ and kept 60-120 minute under nitrogen purging, the content of unreacted MMA is less than 500ppm in product.
This graft copolymer is blended together with the polypropylene (BMWD PP) that available from the MFR of Montell USA Inc. is the wide molecular weight distribution of 1.36g/10min.The amount of the BMWD PP that uses among each embodiment is listed in table 1.The BMWD PP that adds capacity is adjusted to the effective add-on of polymeric monomer that this monomer is 30pph in per 100 parts of polypropylene (BMWD PP adds the polypropylene backbone polymkeric substance).
Rubber is Engage 8150 ethylene/octene available from DuPont-Dow Elastomers, and octene content is 25%.Polyethylene wax is Polywax 3000 polyethylene (PE), and this is a kind of complete saturated homopolymer, and fusing point is 129 ℃, number-average molecular weight (M
n) be 3000, available from Baker Petrolite, PolymersDivision.
The ultraviolet light stabilized masterbatch comprises the calcium salt of Pationic 1240 modifications that 0.05 weight % forms by lactic acid (available from Patco Polymer Additives Division, American Ingredients Company), 0.10%Irganox 1010 oxidation inhibitor (four (methylene radical (3,5-di-tert-butyl-hydroxy phenyl propionic ester)) methane), 0.10%Irgafos 12 oxidation inhibitor (2,2 '; 2 "-nitrilo triethyl-three (3,3 ', 5 ', 5 '-tetra-tert-1,1 '-biphenyl-2,2 '-two bases) phosphorous acid ester), 0.30%Tinuvin 328 oxidation inhibitor (2-(2-hydroxyl-3, the 5-di-tert-pentyl-phenyl)-the 2H benzotriazole), 0.25%Tinuvin 770 oxidation inhibitor (2,2,6,6-tetramethyl--4-piperidyl) sebate) and 0.25%Chimassorb 119 oxidation inhibitor, they all plant chemical limited-liability company available from the vapour Bart.
Pigment is 191067 black masterbatch, available from Ampacet Corporation.Listed content is to be unit with umber in per 100 parts of uncoloured preparations in the table.
Mesh these samples of mixing in the homodromal Werner-Pfleider twin screw extruder at 40mm.Each sample is extruded into pellet.
Be about 440 °F in melt temperature, die temperature is an injection moulding strip in 14 ounces of Van Dorn injection moulding machines of 140.The results are shown in table 1.
At 460 barrel zone temperature, 180 die temperatures and 0.2 " under the injection moulding speed of/s in 5 ounces of Battenfeld injection moulding machines injection moulding be used for cut/scoring test sheet material (4 " * 6 " * 125mil).The results are shown in table 1.
Table 1
| Sample | Comparative example 1 | 1 |
| The graft copolymer type | MMA/MeAc | MMA/MeAc |
| Graft copolymer (weight %) | 44.50 | 42.13 |
| BMWD PP (weight %) | 49.45 | 46.82 |
| Rubber (weight %) | 5.00 | 5.00 |
| Polyethylene wax (weight %) | 0 | 5.00 |
| Stablizer masterbatch (weight %) | 1.05 | 1.05 |
| Black pigment (pph) | 3 | 3 |
| Notched izod impact strength (foot. pound/inch) | 1.3 | 1.2 |
| Tensile strength (psi) | 4904 | 5042 |
| Elongation at break (%) | 174 | 57 |
| Modulus in flexure (0.05 "/min) (kpsi) | 226 | 236 |
| Flexural strength (0.05 "/min) (psi) | 6784 | 6956 |
| Original gloss (20 °) (%) | 78.3 | 81.6 |
| Chrysler crocking glossiness (20 °) (%) | 1.3 | 23 |
| Glossiness keeps (%) | 1.7 | 28.2 |
| Ford crocking glossiness (20 °) (%) | 1 | 6 |
| Glossiness keeps (%) | 2 | 7 |
| Ford 5 finger-type thing cuts (7,6,3,2,0.6N) | 55433 | 44332 |
| Ford 5 finger-type things scratch (7,6,3,2,0.6N) | 45433 | 23232 |
Data show, add low-molecular ethylene polymers and can improve scratch resistance and scratch property, keep good comprehensive physicals simultaneously.
Embodiment 2
The mixture of present embodiment explanation low molecular weight polyethylene or low molecular weight polyethylene and ceramic microsphere is to the scratch resistance of the composition that contains 10% rubber and graft copolymer and the influence of scratch property, and described graft copolymer comprises grafted MMA/MeAc multipolymer on alfon main chain and the main chain.
Graft copolymer makes as described in embodiment 1.
As this graft copolymer and BMWD PP is blended together as described in the embodiment 1.Ceramic microsphere is X-155Zeeospheres, and this is a kind of silica-alumina ceramal, wherein the particle diameter of 90 volume % samples≤7.0-10 micron.This microballoon is handled and available from ZeelanIndustries through Union Carbide A1100 treating compound, Inc.Other component of all of composition is all described identical with embodiment 1.
As described in embodiment 1 sample is mixed and molding, the melt temperature in the test bar moulding process is 460 °F.Physical property test and cut and scoring test the results are shown in table 2.
Table 2
| Sample | Comparative example 1 | 1 | Comparative example 2 | Comparative example 3 | 2 | 3 |
| The graft copolymer type | MMA/MeAc | MMA/MeAc | MMA/MeAc | MMA/MeAc | MMA/MeAc | MMA/MeAc |
| Graft copolymer (weight %) | 42.13 | 39.76 | 39.76 | 37.40 | 37.40 | 35.03 |
| BMWD PP (weight %) | 46.82 | 44.19 | 44.19 | 41.55 | 41.55 | 38.92 |
| Rubber (weight %) | 10.00 | 10.00 | 10.00 | 10.00 | 10.00 | 10.00 |
| Polyethylene wax (weight %) | 0 | 5.00 | 0 | 0 | 5.00 | 5.00 |
| Ceramic microsphere (weight %) | 0 | 0 | 5.00 | 10.00 | 5.00 | 10.00 |
| Stablizer masterbatch (weight %) | 1.05 | 1.05 | 1.05 | 1.05 | 1.05 | 1.05 |
| Black pigment (pph) | 3 | 3 | 3 | 3 | 3 | 3 |
| Notched izod impact strength (foot. pound/inch) | 3.2 | 3.9 | 1.7 | 1.6 | 1.6 | 1.7 |
| Tensile strength (psi) | 4583 | 4700 | 4532 | 4304 | 4578 | 4370 |
| Elongation at break (%) | 194 | 145 | 176 | 173 | 166 | 162 |
| Modulus in flexure (0.05 "/min) (kpsi) | 209 | 216 | 212 | 209 | 213 | 212 |
| Flexural strength (0.05 "/min) (psi) | 6164 | 6305 | 6162 | 5947 | 6162 | 5993 |
| Original gloss (20 °) (%) | 79.3 | 78.3 | 75.2 | 69.7 | 75 | 65 |
| Chrysler crocking glossiness (20 °) (%) | 0.5 | 39 | 5 | 5 | 60 | 55 |
| Glossiness keeps (%) | 0.6 | 49.8 | 6.6 | 7.2 | 80.0 | 84.6 |
| Ford crocking glossiness (20 °) (%) | 3 | 5 | 1 | 1 | 12 | 13 |
| Glossiness keeps (%) | 4 | 6 | 1 | 1 | 16 | 20 |
| Ford 5 finger-type thing cuts (7,6,3,2,0.6N) | 55433 | 34222 | 44322 | 44332 | 34222 | 34222 |
| Ford 5 finger-type things scratch (7,6,3,2,0.6N) | 44422 | 22222 | 44322 | 33322 | 23332 | 23221 |
Data show that the mixture that adds low-molecular ethylene polymers or ethene polymers and ceramic microsphere can improve scratch resistance and scratch property, keeps good comprehensive physicals simultaneously.
Embodiment 3
The mixture of present embodiment explanation low molecular weight polyethylene or low molecular weight polyethylene or low molecular weight polyethylene and ceramic microsphere is to the scratch resistance of the composition that contains 10% rubber and graft copolymer and the influence of scratch property, and described graft copolymer comprises grafted methyl methacrylate/methacrylic acid (MMA/MAA) multipolymer on alfon main chain and the main chain.
Graft copolymer makes as described in embodiment 1, but MAA accounts for 10% of monomer total amount.
As this graft copolymer and BMWD PP is blended together as described in the embodiment 1.Ceramic microsphere is as described in the embodiment 2.Other component of all of composition is all described identical with embodiment 1.
As described in embodiment 1 sample is mixed and molding, the melt temperature in the test bar moulding process is 460 °F.Physical property test and cut and scoring test the results are shown in table 3.
Table 3
| Sample | Comparative example 1 | 1 | Comparative example 2 | Comparative example 3 | 2 | 3 |
| The graft copolymer type | MMA/MAA | MMA/MAA | MMA/MAA | MMA/MAA | MMA/MAA | MMA/MAA |
| Graft copolymer (weight %) | 42.13 | 39.76 | 39.76 | 37.40 | 37.40 | 35.03 |
| BMWD PP (weight %) | 46.82 | 44.19 | 44.19 | 41.55 | 41.55 | 38.92 |
| Rubber (weight %) | 10.00 | 10.00 | 10.00 | 10.00 | 10.00 | 10.00 |
| Polyethylene wax (weight %) | 0 | 5.00 | 0 | 0 | 5.00 | 5.00 |
| Ceramic microsphere (weight %) | 0 | 0 | 5.00 | 10.00 | 5.00 | 10.00 |
| Stablizer masterbatch (weight %) | 1.05 | 1.05 | 1.05 | 1.05 | 1.05 | 1.05 |
| Black pigment (pph) | 3 | 3 | 3 | 3 | 3 | 3 |
| Notched izod impact strength (foot. pound/inch) | 2.3 | 3.2 | 1.7 | 1.3 | 1.6 | 1.4 |
| Tensile strength (psi) | 4652 | 4642 | 4565 | 4466 | 4529 | 4394 |
| Elongation at break (%) | 215 | 151 | 194 | 105 | 81 | 112 |
| Modulus in flexure (0.05 "/min) (kpsi) | 217 | 217 | 216 | 222 | 217 | 219 |
| Flexural strength (0.05 "/min) (psi) | 6393 | 6414 | 6313 | 6280 | 6284 | 6181 |
| Original gloss (20 °) (%) | 77.1 | 76.9 | 75.1 | 68 | 72.5 | 65.6 |
| Chrysler crocking glossiness (20 °) (%) | 0.6 | 18 | 3 | 4 | 62 | 45 |
| Glossiness keeps (%) | 0.8 | 23.4 | 4.0 | 5.9 | 85.5 | 68.6 |
| Ford crocking glossiness (20 °) (%) | 1 | 3 | 18 | 1 | 11 | 15 |
| Glossiness keeps (%) | 1 | 4 | 24 | 1 | 16 | 23 |
| Ford 5 finger-type thing cuts (7,6,3,2,0.6N) | 44332 | 34222 | 44322 | 44222 | 34232 | 34332 |
| Ford 5 finger-type things scratch (7,6,3,2,0.6N) | 23222 | 11111 | 23222 | 23232 | 22222 | 11111 |
Data show that the mixture that adds low-molecular ethylene polymers or ethene polymers and ceramic microsphere can improve scratch resistance and scratch property, keeps good comprehensive physicals simultaneously.
Embodiment 4
Present embodiment explanation low molecular weight polyethylene is to the scratch resistance of the composition that contains 20% rubber and graft copolymer and the influence of scratch property, and described graft copolymer comprises grafted MMA/MeAc multipolymer on alfon main chain and the main chain.
Graft copolymer makes as described in embodiment 1.
As this graft copolymer and BMWD PP is blended together as described in the embodiment 1.Other component of all of composition is all described identical with embodiment 1.
As described in embodiment 1, sample is mixed and molding.Physical property test and cut and scoring test the results are shown in table 4.
Table 4
| Sample | Comparative example 1 | 1 |
| The graft copolymer type | MMA/MeAc | MMA/MeAc |
| Graft copolymer (weight %) | 37.40 | 35.03 |
| BMWD PP (weight %) | 41.55 | 38.92 |
| Rubber (weight %) | 20.00 | 20.00 |
| Polyethylene wax (weight %) | 0 | 5.00 |
| Stablizer masterbatch (weight %) | 1.05 | 1.05 |
| Black pigment (pph) | 3 | 3 |
| Notched izod impact strength (foot. pound/inch) | 13.8 | 15.5 |
| Tensile strength (psi) | 3832 | 3644 |
| Elongation at break (%) | 511 | 499 |
| Modulus in flexure (0.05 "/min) (kpsi) | 165 | 154 |
| Flexural strength (0.05 "/min) (psi) | 4907 | 4586 |
| Original gloss (20 °) (%) | 76.6 | 78.9 |
| Chrysler crocking glossiness (20 °) (%) | 0.4 | 5 |
| Glossiness keeps (%) | 0.5 | 6.3 |
| Ford crocking glossiness (20 °) (%) | 1 | 3 |
| Glossiness keeps (%) | 1 | 4 |
| Ford 5 finger-type thing cuts (7,6,3,2,0.6N) | 54433 | 44332 |
| Ford 5 finger-type things scratch (7,6,3,2,0.6N) | 55543 | 44333 |
Data show, add low-molecular ethylene polymers and can improve scratch resistance and scratch property, keep good comprehensive physicals simultaneously.
Embodiment 5
Present embodiment illustrates various low-molecular ethylene polymers additives to the scratch resistance of the composition of polypropylene (PP) compatilizer that contains 2.5% ceramic microsphere, 1.0% maleinization and graft copolymer and the influence of scratch property, and described graft copolymer comprises grafted MMA/MeAc multipolymer on alfon main chain and the main chain.
Graft copolymer makes as described in embodiment 1.As this graft copolymer and BMWD PP is blended together as described in the embodiment 1.BMWD PP and other components contents are listed in table 5 in the composition.
Rubber, BMWD PP, black pigment and stablizer masterbatch are described identical with embodiment 1.Ceramic microsphere is X92 Zeeospheres, and this is a kind of silica-alumina ceramal, and the particle diameter of the sample of 90 volume %≤6.0-7.4 micron wherein is available from Zeelan Industries, Inc..Toxilic acid grafted polypropylene (PP of maleinization) is the Unite MP 1000 available from Aristech Chemical Corporation.
Polywax 3000 polyethylene (P-wax 3000) are as described in the embodiment 1.Polywax 850 polyethylene (P-wax 850) are complete saturated homopolymer, 107 ℃ of fusing points, M
nBe 850.The fusing point of Unilin 700 long-chain alcohols is 105 ℃, M
nBe 700, available from Baker Petrolite, Polymers Division.The fusing point of the alcohol of Unithox 720 ethoxylations is 106 ℃, M
nWei 875, available from Baker Petrolite, PolymersDivision.The M of Unicid 700 carboxylic acids
nBe 700, fusing point is 110 ℃, available from Baker Petrolite, and Polymers Division.X-5005, X-2025 and X-2026 branched polyethylene wax is available from BakerPetrolite, Polymers Division.
Under meshing in the homodromal Leistritz twin screw extruder extrusion capacity of melt temperature at 232-237 ℃, 250rpm screw speed and 20 Pounds Per Hours, 34mm mixes these samples.In extrusion, vacuumize.
At 460 barrel zone temperature, 180 die temperatures and 0.2 " under the injection moulding speed of/s in 5 ounces of Battenfeld injection moulding machines injection moulding be used for the sheet material of cut/scoring test.The results are shown in table 5.
Table 5
| Sample | Comparative example | 1 | 2 | 3 | 4 | 5 | 6 | 7 | 8 |
| Additive types | - | P-wax 3000 | P-wax 850 | Unilin 700 | Unithox 720 | Unicid 700 | X-5005 | X-2025 | X-2026 |
| MMA/MeAc graft copolymer (weight %) | 42.13 | 38.11 | 38.11 | 38.11 | 38.11 | 38.11 | 38.11 | 38.11 | 38.11 |
| BMWD PP (weight %) | 46.82 | 42.34 | 42.34 | 42.34 | 42.34 | 42.34 | 42.34 | 42.34 | 42.34 |
| Rubber (weight %) | 10 | 10 | 10 | 10 | 10 | 10 | 10 | 10 | 10 |
| Ceramic microsphere (weight %) | 0 | 2.5 | 2.5 | 2.5 | 2.5 | 2.2 | 2.5 | 2.5 | 2.5 |
| Maleinization PP (weight %) | 0 | 1.0 | 1.0 | 1.0 | 1.0 | 1.0 | 1.0 | 1.0 | 1.0 |
| Additive (weight %) | 0 | 5 | 5 | 5 | 5 | 5 | 5 | 5 | 5 |
| Stablizer masterbatch (weight %) | 1.05 | 1.05 | 1.05 | 1.05 | 1.05 | 1.05 | 1.05 | 1.05 | 1.05 |
| Black pigment (pph) | 3 | 3 | 3 | 3 | 3 | 3 | 3 | 3 | 3 |
| Original gloss (20 °) (%) | 79 | 75 | 77 | 76 | 77 | 77 | 78 | 78 | 78 |
| Chrysler crocking glossiness (20 °) (%) | 0.2 | 67 | 55.2 | 68.3 | 64 | 20.2 | 31.2 | 10.9 | 31.1 |
| Glossiness keeps (%) | 0.3 | 89.3 | 71.7 | 89.9 | 83 | 26.2 | 40.0 | 14.0 | 39.9 |
| Ford crocking glossiness (20 °) (%) | 4.3 | 41.4 | 13.4 | 33.0 | 14.1 | 9.6 | 21.0 | 15.0 | 25.4 |
| Glossiness keeps (%) | 5 | 55 | 17 | 43 | 18 | 12 | 27 | 19 | 33 |
| Ford 5 finger-type thing cuts (7,6,3,2,0.6N) | 54332 | 53222 | 53221 | 32121 | 22111 | 42221 | 43221 | 54222 | 53222 |
| Ford 5 finger-type things scratch (7,6,3,2,0.6N) | 33332 | 32222 | 22222 | 11112 | 22222 | 21111 | 22222 | 11111 | 12111 |
Data show that the mixture that adds ceramic microsphere and various low molecular weight polyethylene (straight chain and side chain, functionalized or non-functionalized polyethylene) can improve scratch resistance and scratch property.
Embodiment 6
The low molecular weight polyethylenes with three kinds of different number-average molecular weights of the different amounts of present embodiment explanation are to the scratch resistance of the composition that contains 10% rubber and graft copolymer and the influence of scratch property, and described graft copolymer comprises grafted MMA/MeAc multipolymer on alfon main chain and the main chain.
Graft copolymer makes as described in embodiment 1.
As this graft copolymer and BMWD PP is blended together as described in the embodiment 1.BMWD PP and other components contents are listed in table 6 in the composition.
Polywax 3000 polyethylene are as described in the embodiment 1.Polywax 850 polyethylene are as described in the embodiment 5.Polywax 2000 polyethylene are a kind of complete saturated homopolymer, and fusing point is 126 ℃, M
nBe 2000.Rubber, BMWD PP, black pigment and stablizer masterbatch are as described in the embodiment 1.
Under meshing in the homodromal Leistritz twin screw extruder extrusion capacity of melt temperature at 269-275 ℃, 250rpm screw speed and 20 Pounds Per Hours, 34mm mixes these samples.In extrusion, vacuumize.
Be about 450 °F in melt temperature, die temperature is an injection moulding strip in 5 ounces of Battenfeld injection moulding machines of 150.The sheet material that is used for cut and scoring test as injection moulding as described in the embodiment 1.The results are shown in table 6.
Table 6
| Sample | Comparative example | 1 | 2 | 3 | 4 | 5 | 6 | 7 |
| Graft copolymer (weight %) | 42.13 | 41.66 | 40.95 | 40.24 | 39.77 | 37.4 | 39.7 | 39.77 |
| BMWD PP (weight %) | 46.82 | 46.29 | 45.5 | 44.71 | 44.18 | 41.55 | 44.18 | 44.18 |
| Rubber (weight %) | 10 | 10 | 10 | 10 | 10 | 10 | 10 | 10 |
| P-wax 3000 (weight %) | 0 | 1 | 2.5 | 4 | 5 | 10 | 0 | 0 |
| P-wax 2000 (weight %) | 0 | 0 | 0 | 0 | 0 | 0 | 5 | 0 |
| P-wax 850 (weight %) | 0 | 0 | 0 | 0 | 0 | 0 | 0 | 5 |
| Stablizer masterbatch (weight %) | 1.05 | 1.05 | 1.05 | 1.05 | 1.05 | 1.05 | 1.05 | 1.05 |
| Black pigment (pph) | 3 | 3 | 3 | 3 | 3 | 3 | 3 | 3 |
| Notched izod impact strength (foot. pound/inch) | 2.43 | 2.94 | 2.62 | 2.58 | 4.28 | 2.46 | 2.8 | 2.3 |
| Tensile strength (psi) | 4525 | 4540 | 4460 | 4569 | 4544 | 4510 | 4506 | 4457 |
| Elongation at yield rate (%) | 6.3 | 6.3 | 6.3 | 6.2 | 6.3 | 6.1 | 6.3 | 6.5 |
| Elongation at break (%) | 130 | 142 | 135 | 77 | 67 | 34 | 86 | 143 |
| Modulus in flexure (0.05 "/min) (kpsi) | 224 | 225 | 216 | 222 | 220 | 215 | 216 | 206 |
| Flexural strength (0.05 "/min) (psi) | 6458 | 6484 | 6213 | 6425 | 6342 | 6119 | 6195 | 5979 |
| Original gloss (20 °) (%) | 79 | 79 | 78 | 76 | 78 | 79 | 72 | 79 |
| Chrysler crocking glossiness (20 °) (%) | 0.4 | 0.4 | 0.6 | 17.5 | 24 | 15.2 | 27.3 | 13.9 |
| Glossiness keeps (%) | 0.5 | 0.5 | 0.8 | 23.0 | 30.8 | 19.2 | 37.9 | 17.6 |
| Ford crocking glossiness (20 °) (%) | 1.1 | 1.4 | 5.7 | 5.5 | 3.8 | 4.8 | 4.5 | 4.8 |
| Glossiness keeps (%) | 1 | 2 | 7 | 7 | 5 | 6 | 6 | 6 |
| Ford 5 finger-type thing cuts (7,6,3,2,0.6N) | 55433 | 55432 | 44322 | 44322 | 33222 | 43222 | 32221 | 43211 |
| Ford 5 finger-type things scratch (7,6,3,2,0.6N) | 43321 | 43211 | 33111 | 21111 | 21111 | 11111 | 11111 | 21111 |
Data show that the improvement degree of scratch resistance and scratch property increases with the increase of low molecular weight polyethylene add-on, compares scratch resistance/scratch performance with comparative example simultaneously under the situation of various molecular weight and all improves to some extent.
Embodiment 7
The low molecular weight polyethylenes of the different amounts of present embodiment explanation are to the scratch resistance of the composition of the polypropylene, 10% rubber and the graft copolymer that contain 2.5% ceramic microsphere, 1% maleinization and the influence of scratch property, and described graft copolymer comprises grafted MMA/MeAc multipolymer on alfon main chain and the main chain.
As graft copolymer and BMWD PP is blended together as described in the embodiment 1.As mixing and molded sample as described in the embodiment 6.
The polypropylene compatilizer of ceramic microsphere and maleinization is as described in the embodiment 5.Polyethylene wax is as embodiment 1 described Polywax 3000.Other component of composition is identical with embodiment 6, and content is separately listed in table 7.Cut and scoring test the results are shown in table 7.
Table 7
| Sample | Comparative example | 1 | 2 | 3 | 4 |
| Graft copolymer (weight %) | 40.48 | 40.00 | 39.29 | 38.58 | 38.11 |
| BMWD PP (weight %) | 44.97 | 44.45 | 43.66 | 42.87 | 42.34 |
| Rubber (weight %) | 10 | 10 | 10 | 10 | 10 |
| Ceramic microsphere (weight %) | 2.5 | 2.5 | 2.5 | 2.5 | 2.5 |
| The PP of maleinization (weight %) | 1.0 | 1.0 | 1.0 | 1.0 | 1.0 |
| Polyethylene wax (weight %) | 0 | 1 | 2.5 | 4 | 5 |
| Stablizer masterbatch (weight %) | 1.05 | 1.05 | 1.05 | 1.05 | 1.05 |
| Black pigment (pph) | 3 | 3 | 3 | 3 | 3 |
| Notched izod impact strength (foot. pound/inch) | 2.2 | 2.06 | 2.28 | 2.23 | 2.31 |
| Tensile strength (psi) | 4458 | 4467 | 4450 | 4473 | 4502 |
| Elongation at yield rate (%) | 6.3 | 6.3 | 6.6 | 6.4 | 6.4 |
| Elongation at break (%) | 137 | 107 | 108 | 77 | 58 |
| Modulus in flexure (0.05 "/min) (kpsi) | 218 | 218 | 216 | 217 | 215 |
| Flexural strength (0.05 "/min) (psi) | 6221 | 6214 | 6144 | 6177 | 6171 |
| Original gloss (20 °) (%) | 78 | 77 | 72 | 72 | 76 |
| Chrysler crocking glossiness (20 °) (%) | 0.8 | 1.1 | 1.7 | 33.3 | 53.2 |
| Glossiness keeps (%) | 1.0 | 1.4 | 2.4 | 46.3 | 70.0 |
| Ford crocking glossiness (20 °) (%) | 2.1 | 6.6 | 8.9 | 11.4 | 35.9 |
| Glossiness keeps (%) | 3 | 9 | 12 | 16 | 47 |
| Ford 5 finger-type thing cuts (7,6,3,2,0.6N) | 55432 | 43322 | 43322 | 43322 | 54322 |
| Ford 5 finger-type things scratch (7,6,3,2,0.6N) | 43111 | 32111 | 32111 | 32111 | 43211 |
Data show that the improvement degree of scratch resistance and scratch property increases with the increase of low molecular weight polyethylene add-on.
Embodiment 8
Present embodiment explanation has or does not have the ceramic microsphere of difference amount of polypropylene compatilizer of maleinization to the scratch resistance of the composition that contains 5% low molecular weight polyethylene, 10% rubber and graft copolymer and the influence of scratch property, and described graft copolymer comprises grafted MMA/MeAc multipolymer on alfon main chain and the main chain.
As preparation graft copolymer and graft copolymer and BMWD PP is blended together as described in the embodiment 1.Mesh these samples of mixing in the homodromal Werner-Pfleider twin screw extruder at 40mm.
Be about 450 °F in melt temperature, die temperature is an injection moulding strip in 5 ounces of Battenfeld injection moulding machines of 150.The sheet material that is used for cut and scoring test as injection moulding as described in the embodiment 1.
The polypropylene of ceramic microsphere and maleinization is as described in the embodiment 5.Other component of composition is identical with embodiment 1, and content is separately listed in table 8.Physical property test and cut and scoring test the results are shown in table 8.
Table 8
| Sample | Comparative example 1 | 1 | 2 | 3 |
| Graft copolymer (weight %) | 42.13 | 38.58 | 37.40 | 36.45 |
| BMWD PP (weight %) | 46.82 | 42.87 | 41.55 | 40.50 |
| Rubber (weight %) | 10.00 | 10.00 | 10.00 | 10.00 |
| The PP of maleinization (weight %) | 0 | 0 | 0 | 2.00 |
| Ceramic microsphere (weight %) | 0 | 2.50 | 5.00 | 5.00 |
| Polyethylene wax (weight %) | 0 | 5.00 | 5.00 | 5.00 |
| Stablizer masterbatch (weight %) | 1.05 | 1.05 | 1.05 | 1.05 |
| Black pigment (pph) | 3 | 3 | 3 | 3 |
| Notched izod impact strength (foot. pound/inch) | 4.39 | 2.81 | 2.0 | 2.3 |
| Tensile strength (psi) | 4492 | 4611 | 4370 | 4515 |
| Elongation at break (%) | 278 | 152 | 78 | 54 |
| Elongation at yield rate (%) | 6.76 | 6.4 | 6.5 | 6.6 |
| Modulus in flexure (0.05 "/min) (kpsi) | 210.8 | 217.9 | 214 | 210 |
| Flexural strength (0.05 "/min) (psi) | 6169 | 6261 | 5930 | 6075 |
| Original gloss (20 °) (%) | 79.5 | 77.9 | 73 | 77 |
| Chrysler crocking glossiness (20 °) (%) | 0.3 | 31.8 | 62 | 65 |
| Glossiness keeps (%) | 0.4 | 40.8 | 85 | 84 |
| Ford crocking glossiness (20 °) (%) | 0.9 | 7.4 | 32 | 36 |
| Glossiness keeps (%) | 1.1 | 9.5 | 44 | 47 |
Data show that the improvement degree of scratch resistance and scratch property increases with the increase of ceramic microsphere add-on.The polypropylene that adds maleinization can not reduce the advantage of polyethylene wax and ceramic microsphere mixture.
Embodiment 9
The ceramic microspheres of the different amounts of present embodiment explanation and compatilizer are to the scratch resistance of the composition that contains 5% rubber, 5% polyethylene wax and graft copolymer and the influence of scratch property, and described graft copolymer comprises grafted MMA/MeAc multipolymer on alfon main chain and the main chain.
As preparation graft copolymer and graft copolymer and BMWD PP is blended together as described in the embodiment 1.
Mesh in the homodromal Werner-Pfleider twin screw extruder at 40mm, under the extrusion capacity of 300-310 ℃ of melt temperature, 400-500rpm screw speed and 170-215 Pounds Per Hour, mix these samples.Regulating the extrusion capacity of forcing machine and the melt flow rate (MFR) that rotating speed makes product is 16-18g/10min at 230 ℃/3.8kg.In extrusion, vacuumize.
Be about 425 °F in melt temperature, die temperature is an injection moulding strip in 9 ounces of HPM injection moulding machines of 140.At barrel zone temperature is 475 °F, and die temperature is that 180 and injecting rate are 0.5 " on 5 ounces of Battenfeld injection moulding machines of/s injection moulding be used for the sheet material of cut and scoring test.
Ceramic microsphere is embodiment 5 described X92 Zeeospheres.The polypropylene of maleinization is as described in the embodiment 5.Other component of composition is identical with embodiment 1, and content is separately listed in table 9.Physical property test and cut and scoring test the results are shown in table 9.
Table 9
| Sample | 1 | 2 | 3 | 4 |
| Graft copolymer (weight %) | 42.13 | 41.42 | 40.48 | 38.81 |
| BMWD PP (weight %) | 46.82 | 46.03 | 44.97 | 43.14 |
| Rubber (weight %) | 5 | 5 | 5 | 5 |
| Ceramic microsphere (weight %) | 0 | 1 | 2.5 | 5 |
| The PP of maleinization (weight %) | 0 | 0.5 | 1 | 2 |
| Polyethylene wax (weight %) | 5 | 5 | 5 | 5 |
| Stablizer masterbatch (weight %) | 1.05 | 1.05 | 1.05 | 1.05 |
| Black pigment (pph) | 3 | 3 | 3 | 3 |
| Notched izod impact strength (foot. pound/inch) | 3.8 | 1.5 | 1.5 | 1.4 |
| Modulus in flexure (kpsi) | 202.2 | 233.7 | 241 | 247.9 |
| Flexural strength (kpsi) | 5.81 | 6.81 | 6.91 | 7.05 |
| Original gloss (20 °) (%) | 79.8 | 79.1 | 78.5 | 66.9 |
| Chrysler crocking glossiness (20 °) (%) | 25.5 | 43.8 | 63.4 | 22.5 |
| Glossiness keeps (%) | 32.0 | 55.4 | 80.8 | 33.6 |
| Ford crocking glossiness (20 °) (%) | 13.6 | 21.7 | 32.0 | 21.9 |
| Glossiness keeps (%) | 17 | 27 | 41 | 33 |
| Ford 5 finger-type thing cuts (7,6,3,2,0.6N) | 55332 | 55432 | 44332 | 44332 |
| Ford 5 finger-type things scratch (7,6,3,2,0.6N) | 22222 | 22221 | 22222 | 22221 |
Data show, when having the polypropylene compatilizer of maleinization, add ceramic microsphere and can improve scratch resistance and scratch property.
Embodiment 10
The ceramic microspheres of the different amounts of present embodiment explanation and compatilizer are to the scratch resistance of the composition that contains 10% rubber, 5% polyethylene wax and graft copolymer and the influence of scratch property, and described graft copolymer comprises grafted MMA/MeAc multipolymer on alfon main chain and the main chain.
As preparation graft copolymer and graft copolymer and BMWD PP is blended together as described in the embodiment 1.As mixing and injection moulding sample as described in the embodiment 9.
Ceramic microsphere is embodiment 5 described X92 Zeeospheres, and the polypropylene of maleinization is as described in the embodiment 5.Other component of composition is identical with embodiment 1, and content is separately listed in table 10.Physical property test and cut and scoring test the results are shown in table 10.
Table 10
| Sample | 1 | 2 | 3 | 4 |
| Graft copolymer (weight %) | 39.76 | 39.06 | 38.11 | 36.45 |
| BMWD PP (weight %) | 44.19 | 43.39 | 42.34 | 40.5 |
| Rubber (weight %) | 10 | 10 | 10 | 10 |
| Ceramic microsphere (weight %) | 0 | 1 | 2.5 | 5 |
| The PP of maleinization (weight %) | 0 | 0.5 | 1 | 2 |
| Polyethylene wax (weight %) | 5 | 5 | 5 | 5 |
| Stablizer masterbatch (weight %) | 1.05 | 1.05 | 1.05 | 1.05 |
| Black pigment (pph) | 3 | 3 | 3 | 3 |
| Notched izod impact strength (foot. pound/inch) | 2.9 | 2.4 | 1.8 | 2 |
| Modulus in flexure (kpsi) | 211.7 | 210.7 | 212.8 | 213.6 |
| Flexural strength (kpsi) | 6.15 | 6.14 | 6.15 | 6.13 |
| Original gloss (20 °) (%) | 80 | 79.5 | 76.8 | 76.2 |
| Chrysler crocking glossiness (20 °) (%) | 24.3 | 38.9 | 60.7 | 55.4 |
| Glossiness keeps (%) | 30.4 | 48.9 | 79.0 | 72.7 |
| Ford crocking glossiness (20 °) (%) | 7.4 | 9.9 | 39.4 | 31.1 |
| Glossiness keeps (%) | 9 | 12 | 51 | 41 |
| Ford 5 finger-type thing cuts (7,6,3,2,0.6N) | 55333 | 55332 | 55332 | 55332 |
| Ford 5 finger-type things scratch (7,6,3,2,0.6N) | 22222 | 22221 | 22221 | 22221 |
Data show, even ceramic microsphere and compatibilizer content also can be improved scratch resistance and scratch property when low.
Embodiment 11
The ceramic microspheres of the different amounts of present embodiment explanation and compatilizer are to the scratch resistance of the composition that contains 15% rubber, 5% polyethylene wax and graft copolymer and the influence of scratch property, and described graft copolymer comprises grafted MMA/MeAc multipolymer on alfon main chain and the main chain.
As preparation graft copolymer and graft copolymer and BMWD PP is blended together as described in the embodiment 1.As described in the embodiment 9 with sample mixed together and injection moulding.
Ceramic microsphere is embodiment 5 described X92 Zeeospheres, and the polypropylene of maleinization is as described in the embodiment 5.Other component of composition is identical with embodiment 1, and content is separately listed in table 11.Physical property test and cut and scoring test the results are shown in table 11.
Table 11
| Sample | 1 | 2 | 3 | 4 |
| Graft copolymer (weight %) | 37.4 | 36.69 | 35.74 | 34.08 |
| BMWD PP (weight %) | 41.55 | 40.76 | 39.71 | 37.87 |
| Rubber (weight %) | 15 | 15 | 15 | 15 |
| Ceramic microsphere (weight %) | 0 | 1 | 2.5 | 5 |
| The PP of maleinization (weight %) | 0 | 0.5 | 1 | 2 |
| Polyethylene wax (weight %) | 5 | 5 | 5 | 5 |
| Stablizer masterbatch (weight %) | 1.05 | 1.05 | 1.05 | 1.05 |
| Black pigment (pph) | 3 | 3 | 3 | 3 |
| Notched izod impact strength (foot. pound/inch) | 13 | 10.4 | 12 | 6.2 |
| Modulus in flexure (kpsi) | 180.2 | 189.7 | 187.2 | 194.6 |
| Flexural strength (kpsi) | 5.24 | 5.52 | 5.45 | 5.58 |
| Elongation at break (%) | 438 | 349 | 350 | 300 |
| Original gloss (20 °) (%) | 81.3 | 81 | 78.5 | 77.3 |
| Chrysler crocking glossiness (20 °) (%) | 2.6 | 8.3 | 39.3 | 12.6 |
| Glossiness keeps (%) | 3.2 | 10.2 | 50.1 | 16.3 |
| Ford crocking glossiness (20 °) (%) | 8.2 | 7.3 | 9.7 | 16.0 |
| Glossiness keeps (%) | 10 | 9 | 12 | 21 |
| Ford 5 finger-type thing cuts (7,6,3,2,0.6N) | 55332 | 55332 | 55332 | 55332 |
| Ford 5 finger-type things scratch (7,6,3,2,0.6N) | 22221 | 22221 | 22221 | 22222 |
Data show, even when ceramic microsphere and compatibilizer content are low, also can improve scratch resistance and scratch property.
Embodiment 12
The ceramic microspheres of the different amounts of present embodiment explanation and compatilizer are to the scratch resistance of the composition that contains 20% rubber, 5% polyethylene wax and graft copolymer and the influence of scratch property, and described graft copolymer comprises grafted MMA/MeAc multipolymer on alfon main chain and the main chain.
As preparation graft copolymer and graft copolymer and BMWD PP is blended together as described in the embodiment 1.As mixing and injection moulding sample as described in the embodiment 9.
Ceramic microsphere is embodiment 5 described X92 Zeeospheres, and the polypropylene of maleinization is as described in the embodiment 5.Other component of composition is identical with embodiment 1, and content is separately listed in table 12.Physical property test and cut and scoring test the results are shown in table 12.
Table 12
| Sample | 1 | 2 | 3 | 4 |
| Graft copolymer (weight %) | 35.03 | 34.32 | 33.37 | 31.71 |
| BMWD PP (weight %) | 38.92 | 38.13 | 37.08 | 35.24 |
| Rubber (weight %) | 20 | 20 | 20 | 20 |
| Ceramic microsphere (weight %) | 0 | 1 | 2.5 | 5 |
| The PP of maleinization (weight %) | 0 | 0.5 | 1 | 2 |
| Polyethylene wax (weight %) | 5 | 5 | 5 | 5 |
| Stablizer masterbatch (weight %) | 1.05 | 1.05 | 1.05 | 1.05 |
| Black pigment (pph) | 3 | 3 | 3 | 3 |
| Notched izod impact strength (foot. pound/inch) | 15.9 | 15 | 15.7 | 14.5 |
| Modulus in flexure (kpsi) | 164 | 166.7 | 154.3 | 165.1 |
| Flexural strength (kpsi) | 4.81 | 4.84 | 4.49 | 4.76 |
| Original gloss (20 °) (%) | 78.2 | 77 | 78 | 76 |
| Chrysler crocking glossiness (20 °) (%) | 5.9 | 6.8 | 13.8 | 20.7 |
| Glossiness keeps (%) | 7.5 | 8.8 | 17.7 | 27.2 |
| Ford crocking glossiness (20 °) (%) | 5.1 | 7.8 | 10.6 | 8.1 |
| Glossiness keeps (%) | 7 | 10 | 14 | 11 |
| Ford 5 finger-type thing cuts (7,6,3,2,0.6N) | 55443 | 55332 | 55332 | 55332 |
| Ford 5 finger-type things scratch (7,6,3,2,0.6N) | 22222 | 22221 | 22222 | 22221 |
Data show, even ceramic microsphere and compatibilizer content also can be improved scratch resistance and scratch property when low.
Embodiment 13
The ceramic microsphere of the band treating compounds of two kinds of different amounts of present embodiment explanation and the compatilizer of different amounts are to the scratch resistance of the composition that contains 10% rubber, 5% polyethylene wax and graft copolymer and the influence of scratch property, and described graft copolymer comprises grafted MMA/MeAc multipolymer on alfon main chain and the main chain.
As preparation graft copolymer and graft copolymer and BMWD PP is blended together as described in the embodiment 1.
Mesh in the homodromal Leistritz twin screw extruder at 34mm, under the extrusion capacity of 250 ℃ of melt temperatures, 250rpm screw speed and 23 Pounds Per Hours, mix these samples.In extrusion, vacuumize.
At barrel zone temperature is 485 °F, and die temperature is that " the injecting rate injection moulding of/s is used for the sheet material of cut/scoring test with 0.5 in 5 ounces of Battenfeld injection moulding machines of 180.
X-292 Zeeosphere ceramic microsphere is the silica-alumina ceramal of handling through Union Carbide A 1100 treating compounds, the wherein particle diameter of 90 volume % samples≤5.0-6.2 micron.X-293 Zeeosphere ceramic microsphere is the silica-alumina ceramal of handling through Union Carbide A 1100 treating compounds, the wherein particle diameter of 90 volume % samples≤6.0-7.4 micron.Both are all available from Zeelan Industries, Inc.
The polypropylene of maleinization is as described in the embodiment 5.Other component of composition is identical with embodiment 1, and content is separately listed in table 13.Cut and scoring test the results are shown in table 13.
Table 13
| Sample | 1 | 2 | 3 | 4 | 5 | 6 | 7 |
| Graft copolymer (weight %) | 39.76 | 39.05 | 38.11 | 36.45 | 39.05 | 38.11 | 36.45 |
| BMWD PP (weight %) | 44.19 | 43.4 | 42.34 | 40.5 | 43.4 | 42.34 | 40.5 |
| Rubber (weight %) | 10 | 10 | 10 | 10 | 10 | 10 | 10 |
| Ceramic microsphere (X292) (weight %) | 0 | 1 | 2.5 | 5 | 0 | 0 | 0 |
| Ceramic microsphere (X293) (weight %) | 0 | 0 | 0 | 0 | 1 | 2.5 | 5 |
| The PP of maleinization (weight %) | 0 | 0.5 | 1 | 2 | 0.5 | 1 | 2 |
| Polyethylene wax (weight %) | 5 | 5 | 5 | 5 | 5 | 5 | 5 |
| Stablizer masterbatch (weight %) | 1.05 | 1.05 | 1.05 | 1.05 | 1.05 | 1.05 | 1.05 |
| Black pigment (pph) | 3 | 3 | 3 | 3 | 3 | 3 | 3 |
| Original gloss (20 °) (%) | 82.7 | 81.4 | 79.9 | 75.6 | 79 | 78.4 | 74.5 |
| Chrysler crocking glossiness (20 °) (%) | 23.4 | 52.0 | 65.8 | 60.4 | 62.5 | 69.2 | 44.3 |
| Glossiness keeps (%) | 28.3 | 64 | 82.8 | 79.9 | 79.1 | 88.3 | 59.5 |
| Ford crocking glossiness (20 °) (%) | 4.5 | 9.9 | 13.9 | 16.4 | 18.5 | 12.8 | 18.8 |
| Glossiness keeps (%) | 5.4 | 12.2 | 17.4 | 21.7 | 23.4 | 16.3 | 25.2 |
| Ford 5 finger-type thing cuts (7,6,3,2,0.6N) | 53332 | 53332 | 54432 | 54432 | 54432 | 54432 | 53323 |
| Ford 5 finger-type things scratch (7,6,3,2,0.6N) | 22221 | 22222 | 22122 | 22221 | 32222 | 22221 | 51431 |
Data show that the diameter of ceramic microsphere does not have obvious influence to scratch resistance and scratch property.
Embodiment 14
Present embodiment explanation different amount X-61 Zeeosphere ceramic microspheres and compatilizer are to the scratch resistance of the composition that contains 10% rubber, 5% polyethylene wax and graft copolymer and the influence of scratch property, and described graft copolymer comprises grafted MMA/MeAc multipolymer on alfon main chain and the main chain.
As preparation graft copolymer and graft copolymer and BMWD PP is blended together as described in the embodiment 1.As mixing and injection moulding sample as described in the embodiment 13.
X-61 Zeeosphere ceramic microsphere is the silica-alumina ceramal, and the particle diameter of 90 volume % samples≤4.2-5.2 micron wherein is available from Zeelan Industries, Inc.The polypropylene of maleinization is as described in the embodiment 5.Other component of composition is identical with embodiment 1, and content is separately listed in table 14.Cut and scoring test the results are shown in table 14.
Table 14
| Sample | 1 | 2 | 3 | 4 |
| Graft copolymer (weight %) | 39.76 | 39.05 | 38.11 | 36.45 |
| BMWD PP (weight %) | 44.19 | 43.4 | 42.34 | 40.5 |
| Rubber (weight %) | 10 | 10 | 10 | 10 |
| Ceramic microsphere (X-61) (weight %) | 0 | 1 | 2.5 | 5 |
| The PP of maleinization (weight %) | 0 | 0.5 | 1 | 2 |
| Polyethylene wax (weight %) | 5 | 5 | 5 | 5 |
| Stablizer masterbatch (weight %) | 1.05 | 1.05 | 1.05 | 1.05 |
| Black pigment (pph) | 3 | 3 | 3 | 3 |
| Original gloss (20 °) (%) | 82.7 | 80.2 | 80 | 77 |
| Chrysler crocking glossiness (20 °) (%) | 23.4 | 28.5 | 59.6 | 63.9 |
| Glossiness keeps (%) | 28.3 | 35.5 | 74.5 | 83 |
| Ford crocking glossiness (20 °) (%) | 4.5 | 6.6 | 9.6 | 12.7 |
| Glossiness keeps (%) | 5.4 | 8.2 | 12 | 16.5 |
| Ford 5 finger-type thing cuts (7,6,3,2,0.6N) | 53332 | 53323 | 53323 | 53323 |
| Ford 5 finger-type things scratch (7,6,3,2,0.6N) | 22221 | 51431 | 51431 | 52432 |
Data show, little ceramic microsphere is effectively, and scratch and scratch property is improved with the increase of microballoon add-on.
Embodiment 15
Various inorganic microspheress are used in the present embodiment explanation, the polypropylene coupling agent that uses or do not use maleinization is to the scratch resistance of the composition that contains 10% rubber, 5% polyethylene wax and graft copolymer and the influence of scratch property, and described graft copolymer comprises grafted MMA/MeAc multipolymer on alfon main chain and the main chain.
As preparation graft copolymer and graft copolymer and BMWD PP is blended together as described in the embodiment 1.The mixing of sample is identical with embodiment 5, but melt temperature is about 240 ℃.Sheet material as injection moulding cut/scoring test as described in the embodiment 1.
BMWD PP, rubber, polyethylene wax, stablizer masterbatch and black pigment are as described in the embodiment 1.The polypropylene of maleinization is as described in the embodiment 5.White pigment is RCL 6 white pigments, available from Millenium.
W210 Zeeosphere ceramic microsphere is the alkali metal aluminosilicate ceramic microsphere, particle diameter≤11 of 90 volume % samples micron wherein, and it is available from Zeelan Inductries, Inc.X-273 Zeeosphere ceramic microsphere is the alkali metal aluminosilicate ceramic microsphere, wherein the particle diameter of 90 volume % samples≤6.0-7.4 micron.It is also available from Zeelan Inductries, Inc.90 weight % are less than 15 microns, available from Potters Industries Inc in the size distribution of Spheriglass 6000 glass spheres.
Each components contents and cut and scoring test the results are shown in table 15.
Table 15
| Sample | 1 | 2 | 3 | 4 | 5 | 6 | 7 |
| Graft copolymer (weight %) | 39.77 | 38.11 | 38.11 | 39.29 | 39.77 | 38.11 | 38.11 |
| BMWD PP (weight %) | 44.18 | 42.34 | 42.34 | 43.66 | 44.18 | 42.34 | 42.34 |
| Rubber (weight %) | 10 | 10 | 10 | 10 | 10 | 10 | 10 |
| Ceramic microsphere (W210) (weight %) | - | 2.5 | - | - | - | 2.5 | - |
| Ceramic microsphere (W273) (weight %) | - | - | 2.5 | - | - | - | 2.5 |
| Glass microsphere (weight %) | - | - | - | 2.5 | - | - | - |
| The PP of maleinization (weight %) | - | 1 | 1 | 1 | - | 1 | 1 |
| Polyethylene wax (weight %) | 5 | 5 | 5 | 5 | 5 | 5 | 5 |
| Stablizer masterbatch (weight %) | 1.05 | 1.05 | 1.05 | 1.05 | 1.05 | 1.05 | 1.05 |
| Black pigment (pph) | - | - | - | - | 3 | 3 | 3 |
| White pigment (pph) | 3 | 3 | 3 | 3 | - | - | - |
| Original gloss (20 °) (%) | 79.2 | 79.4 | 79.3 | 79.5 | 77.4 | 77.4 | 78 |
| Chrysler crocking glossiness (20 °) (%) | 17.7 | 56.7 | 56.4 | 65.2 | 12.4 | 43.7 | 35.6 |
| Glossiness keeps (%) | 22.3 | 71.4 | 71.1 | 82 | 16 | 56.5 | 45.6 |
| Ford crocking glossiness (20 °) (%) | 8.2 | 18.7 | 25.4 | 28 | 4.5 | 12.5 | 9.8 |
| Glossiness keeps (%) | 10.4 | 23.6 | 22 | 35.2 | 5.8 | 16.1 | 12.6 |
| Ford 5 finger-type thing cuts (7,6,3,2,0.6N) | 44322 | 44432 | 44332 | 44321 | 44332 | 44322 | 44322 |
| Ford 5 finger-type things scratch (7,6,3,2,0.6N) | 11221 | 11111 | 11111 | 11111 | 11111 | 11111 | 11111 |
Data show, add two kinds of alkali metal aluminosilicate ceramic microspheres and add glass microsphere and all can improve scratch resistance/scratch performance.
Those of ordinary skill in the art can easily learn further feature of the present invention, advantage and example after the description on read.Therefore, although specific examples of the present invention has been carried out quite detailed description, under the situation that does not depart from described and claimed spirit and scope of the invention, can carry out changes and improvements to these examples.
Claims (11)
1. composition, it comprises by weight:
(a) a kind of graft copolymer, it comprises propylene polymer main chain, graft copolymerization has at least a vinyl monomer that can carry out radical polymerization on this main chain, described vinyl monomer is vinylformic acid, acrylate, methacrylic acid and methacrylic ester, and the content of polymerization single polymerization monomer is 10-120 part in per 100 parts of amphoteric polymeric materials; With
(b) a kind of additive, it is selected from, gross weight by composition, (i) at least a number-average molecular weight of 0.5%-10% is low-molecular ethylene polymers or its functionalized derivative of 300-5000, derivative or its phosphoric acid ester that described functionalized derivative is hydroxylation or ethoxylation, perhaps monocarboxylic derivative or toxilic acid grafted linear ethylene polymkeric substance, the (ii) mixture of the low-molecular ethylene polymers described in (1) 0.5%-10% at least a (i) and (2) 0.5-10% inorganic microspheres, described inorganic microspheres comprises at least a silica-alumina ceramal, alkali metal aluminosilicate pottery and glass
Described amphoteric polymeric material is selected from:
(A) isotactic index is greater than 80 alfon;
(B) propylene and a kind of multipolymer that is selected from the ethene and the alkene of alpha-olefin with 4-10 carbon atom, condition is when described alkene is ethene, the maximum level of polymerising ethylene is 10%, when described alkene is when having the alpha-olefin of 4-10 carbon atom, its polymeric maximum level is 20 weight %, and the isotactic index of described multipolymer is greater than 85;
(C) propylene and two kinds of terpolymers that are selected from the ethene and the alkene of alpha-olefin with 4-8 carbon atom, condition is that the maximum polymerization content with alpha-olefin of 4-8 carbon atom is 20 weight %, when ethene is one of the alkene of copolymerization, the maximum level of polymerising ethylene is 5 weight %, and the isotactic index of described terpolymer is greater than 85;
(D) a kind of olefin polymer compositions, it comprises:
(i) 10-60 weight % isotactic index is greater than 80 alfon, or be selected from (1) propylene and ethene, (2) propylene, ethene and have the alpha-olefin of 4-8 carbon atom, (3) propylene and monomeric multipolymer with alpha-olefin of 4-8 carbon atom, the content of polypropylene is greater than 85 weight % in the multipolymer, and isotactic index is greater than 85;
(ii) 5-25 weight % ethene and propylene or have the multipolymer of the alpha-olefin of 4-8 carbon atom are insoluble to dimethylbenzene at this multipolymer of room temperature; With
(iii) 30-70 weight % is selected from (1) ethene and propylene, (2) ethene, propylene and have the alpha-olefin of 4-8 carbon atom, (3) ethene and monomeric elastocopolymer with alpha-olefin of 4-8 carbon atom, the polymeric ethylene content is less than 70 weight %, this multipolymer is dissolved in dimethylbenzene at ambient temperature, and the limiting viscosity that records under 135 ℃ in naphthane is 1.5-4.0dl/g;
Wherein (ii) and total amount (iii) account for the 50-90% of olefin polymer compositions total amount, weight ratio (ii)/(iii) is less than 0.4, and described composition makes by two-stage polymerization at least, its modulus in flexure is less than 150MPa; With
(E) a kind of thermoplastic olefin, it comprises:
(i) the 10-60% isotactic index is greater than 80 alfon, or be selected from (1) ethene and propylene, (2) ethene, propylene and have the alpha-olefin of 4-8 carbon atom, (3) ethene and monomeric multipolymer with alpha-olefin of 4-8 carbon atom, the content of polymeric propylene is greater than 85% in this multipolymer, and isotactic index is greater than 85;
(ii) 20-60% is selected from (1) ethene and propylene, (2) ethene, propylene and have the alpha-olefin of 4-8 carbon atom, (3) ethene and monomeric amorphous copolymer with alpha-olefin of 4-8 carbon atom, the content of polymeric ethene is less than 70%, and this multipolymer is dissolved in dimethylbenzene at ambient temperature; With
(iii) 3-40% ethene and propylene or have the multipolymer of the alpha-olefin of 4-8 carbon atom are insoluble to dimethylbenzene at this multipolymer of envrionment temperature;
Wherein the modulus in flexure of this thermoplastic olefin is greater than 150MPa, but less than 1200MPa.
2. composition as claimed in claim 1 is characterized in that described ethene and the monomeric elastocopolymer with alpha-olefin of 4-8 carbon atom contain 0.5-10% polymeric diene.
3. composition as claimed in claim 1 is characterized in that described amphoteric polymeric material is an alfon.
4. as any one described composition among the claim 1-3, it is characterized in that described vinyl monomer is selected from (a) methyl methacrylate and methyl acrylate and (b) methyl methacrylate and methacrylic acid.
5. as any one described composition among the claim 1-3, by composition total weight, it also comprises 0.2-4% compatilizer and at least a rubber components of 2-30%, described compatilizer comprises acid-functionalized propene polymer, described rubber components is selected from (a) olefin copolymer rubber, (b) mono alkenyl aromatic hydrocarbon conjugated diene block copolymer and (c) nuclear-shell rubber.
6. as any one described composition among the claim 1-3, by composition total weight, it also comprises 15-50%M
w/ M
nPropene polymer for the wide molecular weight distribution of 5-60.
7. composition as claimed in claim 6 is characterized in that described ethene and the monomeric elastocopolymer with alpha-olefin of 4-8 carbon atom contain 0.5-10% polymeric diene.
8. one kind is improved the scratch resistance of graft copolymer and the method for scratch property, it comprises with following (a) with (b) and mixing, (a) a kind of graft copolymer, it comprises propylene polymer main chain, graft polymerization has at least a vinyl monomer that can carry out radical polymerization on this main chain, described vinyl monomer is vinylformic acid, acrylate, methacrylic acid and methacrylic ester, and the content of polymerization single polymerization monomer is 10-120 part in per 100 parts of amphoteric polymeric materials; (b) a kind of additive, it is selected from, gross weight by composition, (i) at least a number-average molecular weight of 0.5%-10% is low-molecular ethylene polymers or its functionalized derivative of 300-5000, derivative or its phosphoric acid ester that described functionalized derivative is hydroxylation or ethoxylation, perhaps monocarboxylic derivative or toxilic acid grafted linear ethylene polymkeric substance, the (ii) mixture of the low-molecular ethylene polymers described in (1) 0.5%-10% at least a (i) and (2) 0.5-10% inorganic microspheres, described inorganic microspheres comprises at least a silica-alumina ceramal, alkali metal aluminosilicate pottery and glass
Described amphoteric polymeric material is selected from:
(A) isotactic index is greater than 80 alfon;
(B) propylene and a kind of multipolymer that is selected from the ethene and the alkene of alpha-olefin with 4-10 carbon atom, condition is when described alkene is ethene, the maximum level of polymerising ethylene is 10%, when described alkene is when having the alpha-olefin of 4-10 carbon atom, its polymeric maximum level is 20 weight %, and the isotactic index of described multipolymer is greater than 85;
(C) propylene and two kinds of terpolymers that are selected from the ethene and the alkene of alpha-olefin with 4-8 carbon atom, condition is that the maximum polymerization content with alpha-olefin of 4-8 carbon atom is 20 weight %, when ethene is one of the alkene of copolymerization, the maximum level of polymerising ethylene is 5 weight %, and the isotactic index of described terpolymer is greater than 85;
(D) a kind of olefin polymer compositions, it comprises:
(i) 10-60 weight % isotactic index is greater than 80 alfon, or be selected from (1) propylene and ethene, (2) propylene, ethene and have the alpha-olefin of 4-8 carbon atom, (3) propylene and monomeric multipolymer with alpha-olefin of 4-8 carbon atom, the content of polypropylene is greater than 85 weight % in the multipolymer, and isotactic index is greater than 85;
(ii) 5-25 weight % ethene and propylene or have the multipolymer of the alpha-olefin of 4-8 carbon atom are insoluble to dimethylbenzene at this multipolymer of envrionment temperature; With
(iii) 30-70 weight % is selected from (1) ethene and propylene, (2) ethene, propylene and have the alpha-olefin of 4-8 carbon atom, (3) ethene and monomeric elastocopolymer with alpha-olefin of 4-8 carbon atom, the polymeric ethylene content is less than 70 weight %, this multipolymer is dissolved in dimethylbenzene at ambient temperature, and the limiting viscosity that records under 135 ℃ in naphthane is 1.5-4.0dl/g;
Wherein (ii) and total amount (iii) account for the 50-90% of olefin polymer compositions total amount, weight ratio (ii)/(iii) is less than 0.4, and described composition makes by two-stage polymerization at least, its modulus in flexure is less than 150MPa; With
(E) a kind of thermoplastic olefin, it comprises:
(i) the 10-60% isotactic index is greater than 80 alfon, or be selected from (1) ethene and propylene, (2) ethene, propylene and have the alpha-olefin of 4-8 carbon atom, (3) ethene and monomeric multipolymer with alpha-olefin of 4-8 carbon atom, the content of polymeric propylene is greater than 85% in this multipolymer, and isotactic index is greater than 85;
(ii) 20-60% is selected from (1) ethene and propylene, (2) ethene, propylene and have the alpha-olefin of 4-8 carbon atom, (3) ethene and monomeric amorphous copolymer with alpha-olefin of 4-8 carbon atom, the content of polymeric ethene is less than 70%, and this multipolymer is dissolved in dimethylbenzene at ambient temperature; With
(iii) 3-40% ethene and propylene or have the multipolymer of the alpha-olefin of 4-8 carbon atom are insoluble to dimethylbenzene at this multipolymer of room temperature;
Wherein the modulus in flexure of this thermoplastic olefin is greater than 150MPa, but less than 1200MPa.
9. method as claimed in claim 8 is characterized in that described ethene and the monomeric elastocopolymer with alpha-olefin of 4-8 carbon atom contain 0.5-10% polymeric diene.
10. method as claimed in claim 8 or 9 is characterized in that by composition total weight, adds the 0.2-4% compatilizer, and this compatilizer comprises acid-functionalized propene polymer.
11. the goods made from the described composition of claim 1.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US09/213,576 US6177515B1 (en) | 1998-12-17 | 1998-12-17 | Polypropylene graft copolymers with improved scratch and mar resistance |
| US09/213,576 | 1998-12-17 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1294614A CN1294614A (en) | 2001-05-09 |
| CN1161412C true CN1161412C (en) | 2004-08-11 |
Family
ID=22795644
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB998043346A Expired - Fee Related CN1161412C (en) | 1998-12-17 | 1999-12-08 | Polypropylene graft copolymers with improved scratch and mar resistance |
Country Status (13)
| Country | Link |
|---|---|
| US (1) | US6177515B1 (en) |
| EP (1) | EP1056807B1 (en) |
| JP (1) | JP2002532602A (en) |
| KR (1) | KR100624866B1 (en) |
| CN (1) | CN1161412C (en) |
| AT (1) | ATE287927T1 (en) |
| AU (1) | AU762515B2 (en) |
| BR (1) | BR9908014A (en) |
| CA (1) | CA2320954C (en) |
| DE (1) | DE69923433T2 (en) |
| ID (1) | ID26122A (en) |
| NO (1) | NO20004086L (en) |
| WO (1) | WO2000036012A1 (en) |
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|---|---|---|---|---|
| US6465571B1 (en) * | 2000-05-03 | 2002-10-15 | Solvay Engineered Polymers | Engineered polyolefin materials with enhanced properties |
| US6667367B1 (en) * | 2000-10-10 | 2003-12-23 | Basell Poliolefine Italia S.P.A. | Directly paintable polypropylene graft copolymers |
| FR2831794B1 (en) * | 2001-11-05 | 2004-02-13 | Depuy France | METHOD FOR SELECTING KNEE PROSTHESIS ELEMENTS AND DEVICE FOR IMPLEMENTING SAME |
| US7291676B2 (en) * | 2002-09-17 | 2007-11-06 | Basell Poliolefine Italia S.P.A. | Polyolefin composition with improved abrasion resistance |
| US20060020086A1 (en) * | 2002-09-19 | 2006-01-26 | Dennis Smith | Ionomer modified polypropylene compound for superior scratch performance,low blushing and molded in color with controllable gloss |
| AU2003275601A1 (en) * | 2002-10-25 | 2004-05-13 | Nof Corporation | Graft copolymer, composition containing the same and molded object thereof, and process for producing the same |
| JP2007536396A (en) * | 2004-05-05 | 2007-12-13 | ダウ グローバル テクノロジーズ インコーポレイティド | Scratch-resistant propylene polymer composition |
| US20070244234A1 (en) * | 2004-06-14 | 2007-10-18 | Polyone Corporation | Durable and Low Friction Thermoplastic Elastomer Compositions |
| US7390574B2 (en) * | 2004-07-07 | 2008-06-24 | Ciba Specialty Chemicals Corporation | Scratch resistant polyolefins |
| US20070040292A1 (en) * | 2005-08-22 | 2007-02-22 | Fina Technology, Inc. | Polypropylene composition for high gloss retention |
| US20070232757A1 (en) * | 2006-04-03 | 2007-10-04 | Kevin Cai | Mar resistant, glossy thermoplastic polyolefin blends and articles |
| US8080607B2 (en) | 2006-08-16 | 2011-12-20 | Dow Global Technologies Llc | Polymeric material and process for forming and using same |
| US7589138B2 (en) * | 2006-12-05 | 2009-09-15 | Fina Technology, Inc. | Injection molding process |
| KR100804826B1 (en) * | 2006-12-08 | 2008-02-20 | 주식회사 엘지화학 | Olefin-based resin composition for decoration sheets and decoration sheets using the same |
| US7862671B2 (en) * | 2007-01-11 | 2011-01-04 | Dow Global Technologies Inc. | Welding of a polymeric material and structures formed thereby |
| ATE466049T1 (en) * | 2007-12-18 | 2010-05-15 | Borealis Tech Oy | CABLE LAYER MADE OF MODIFIED SOFT POLYPROPYLENE |
| JP2012504687A (en) * | 2008-10-02 | 2012-02-23 | ダウ グローバル テクノロジーズ エルエルシー | Glossy resin and method for producing the same |
| BRPI1005329B1 (en) | 2009-01-30 | 2019-06-18 | Dow Global Technologies Llc | POLYMERIC COMPOSITION, COMPLETED THERMOPLASTIC POLYOLEFIN COMPOSITION AND PROCESS FOR THE MANUFACTURE OF A MOLDED ARTICLE |
| CN102532683A (en) * | 2010-12-16 | 2012-07-04 | 上海普利特复合材料股份有限公司 | Novel scratch-proof polypropylene material and preparation method thereof |
| US9914790B2 (en) * | 2014-10-06 | 2018-03-13 | Hercules Llc | Low molecular weight graft polymer for scale inhibitor |
| CN115521566B (en) * | 2022-11-28 | 2023-03-28 | 广州鹿山新材料股份有限公司 | Nylon toughening agent and preparation method and application thereof |
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| GB1546726A (en) | 1975-06-20 | 1979-05-31 | Toyo Ink Mfg Co | Coatings on interior surfaces of metallic cans and on surfaces of metallics sheet material for cans |
| NL8003192A (en) | 1980-05-31 | 1982-01-04 | Stamicarbon | BIAXIALLY PROVIDED POLYPROPENE PLASTIC PRODUCTS AND METHOD FOR MANUFACTURING SUCH ARTICLES. |
| JPS5911346A (en) * | 1982-07-12 | 1984-01-20 | Showa Denko Kk | Method for treating propylene polymer |
| JPS60212440A (en) * | 1984-04-05 | 1985-10-24 | Mitsubishi Petrochem Co Ltd | Glass-fiber reinforced resin composition |
| CA1292819C (en) * | 1984-10-09 | 1991-12-03 | Toshiki Doi | Polyolefin composition and method of coating molded article obtained therefrom |
| JPS6456750A (en) * | 1987-05-22 | 1989-03-03 | Mitsui Petrochemical Ind | Reinforced thermoplastic polymer composition |
| US5155160A (en) | 1988-05-02 | 1992-10-13 | James River Ii, Inc. | Polyolefin films having improved barrier properties |
| JP2679147B2 (en) * | 1988-09-08 | 1997-11-19 | 住友化学工業株式会社 | Resin composition |
| JP2584663B2 (en) * | 1988-11-08 | 1997-02-26 | 宇部興産株式会社 | Reinforced polypropylene composition |
| US5262471A (en) | 1988-11-21 | 1993-11-16 | Fuji Photo Film Co., Ltd. | Method of preparing packaging material for photographic photosensitive material and masterbatch therefor |
| JPH0645734B2 (en) | 1988-11-30 | 1994-06-15 | 豊田合成株式会社 | Fiber-reinforced polypropylene resin composition |
| KR950007662B1 (en) * | 1991-12-24 | 1995-07-14 | 주식회사럭키 | Polyolefin resin composition(i) having excellent coating |
| US5286791A (en) * | 1992-05-29 | 1994-02-15 | Himont Incorporated | Impact modified graft copolymer compositions containing broad molecular weight distribution polypropylene |
| NO309384B1 (en) * | 1995-01-16 | 2001-01-22 | Borealis Holding As | Polyolefin alloy with improved surface hardness and scratch resistance |
| US5773510A (en) * | 1995-03-30 | 1998-06-30 | Xerox Corporation | Processes for the preparation of branched polymers |
| US6048942A (en) | 1996-09-30 | 2000-04-11 | Montell North America Inc. | Thermoplastic olefin articles having high surface gloss and mar resistance |
| US5859104A (en) * | 1996-12-19 | 1999-01-12 | Montell North America Inc. | Retarding depolymerization of poly(methyl methacrylate) grafted onto a propylene polymer |
-
1998
- 1998-12-17 US US09/213,576 patent/US6177515B1/en not_active Expired - Fee Related
-
1999
- 1999-12-08 KR KR1020007008960A patent/KR100624866B1/en not_active IP Right Cessation
- 1999-12-08 AU AU14034/00A patent/AU762515B2/en not_active Ceased
- 1999-12-08 EP EP99973412A patent/EP1056807B1/en not_active Expired - Lifetime
- 1999-12-08 WO PCT/IB1999/001964 patent/WO2000036012A1/en active IP Right Grant
- 1999-12-08 CA CA002320954A patent/CA2320954C/en not_active Expired - Fee Related
- 1999-12-08 ID IDW20001838A patent/ID26122A/en unknown
- 1999-12-08 BR BR9908014-1A patent/BR9908014A/en not_active Application Discontinuation
- 1999-12-08 DE DE69923433T patent/DE69923433T2/en not_active Expired - Lifetime
- 1999-12-08 CN CNB998043346A patent/CN1161412C/en not_active Expired - Fee Related
- 1999-12-08 JP JP2000588266A patent/JP2002532602A/en active Pending
- 1999-12-08 AT AT99973412T patent/ATE287927T1/en not_active IP Right Cessation
-
2000
- 2000-08-16 NO NO20004086A patent/NO20004086L/en not_active Application Discontinuation
Also Published As
| Publication number | Publication date |
|---|---|
| CA2320954C (en) | 2006-10-24 |
| NO20004086L (en) | 2000-10-16 |
| WO2000036012A1 (en) | 2000-06-22 |
| NO20004086D0 (en) | 2000-08-16 |
| ID26122A (en) | 2000-11-23 |
| CN1294614A (en) | 2001-05-09 |
| DE69923433T2 (en) | 2006-02-16 |
| ATE287927T1 (en) | 2005-02-15 |
| EP1056807B1 (en) | 2005-01-26 |
| US6177515B1 (en) | 2001-01-23 |
| DE69923433D1 (en) | 2005-03-03 |
| BR9908014A (en) | 2000-10-24 |
| AU762515B2 (en) | 2003-06-26 |
| KR100624866B1 (en) | 2006-09-14 |
| AU1403400A (en) | 2000-07-03 |
| CA2320954A1 (en) | 2000-06-22 |
| KR20010040977A (en) | 2001-05-15 |
| EP1056807A1 (en) | 2000-12-06 |
| JP2002532602A (en) | 2002-10-02 |
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